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Ink Jet Yellow Ink, Ink Set, Ink Jet Recording Method, Ink Cartridge, Recording Unit, And Ink Jet Recording Apparatus - Patent 7241332

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Ink Jet Yellow Ink, Ink Set, Ink Jet Recording Method, Ink Cartridge, Recording Unit, And Ink Jet Recording Apparatus - Patent 7241332 Powered By Docstoc
					


United States Patent: 7241332


































 
( 1 of 1 )



	United States Patent 
	7,241,332



 Yoshizawa
,   et al.

 
July 10, 2007




Ink jet yellow ink, ink set, ink jet recording method, ink cartridge,
     recording unit, and ink jet recording apparatus



Abstract

To provide an ink jet yellow ink to be used in combination with ink
     excellent in light resistance and environmental gas resistance with a
     color fading balance with respect to light and an environmental gas
     between the inks uniformized. The ink jet yellow ink is an ink jet yellow
     ink to be used for forming an image together with a cyan ink comprising a
     compound represented by a general formula (1) or a compound represented
     by a general formula (2) as a coloring material, the ink jet yellow ink
     comprising: at least one kind of coloring material selected from the
     following A group; and at least one kind of coloring material selected
     from the following B group. A group: C.I. Direct Yellow 132 and C.I.
     Direct Yellow 173 B group: C.I. Direct Yellow 142, C.I. Direct Yellow 86,
     and a compound represented by a general formula (3).


 
Inventors: 
 Yoshizawa; Jun (Tokyo, JP), Sato; Shin-ichi (Kawasaki, JP), Nakamura; Kunihiko (Gotenba, JP) 
 Assignee:


Canon Kabushiki Kaisha
 (Tokyo, 
JP)





Appl. No.:
                    
11/339,651
  
Filed:
                      
  January 26, 2006

 Related U.S. Patent Documents   
 

Application NumberFiling DatePatent NumberIssue Date
 PCT/JP2005/014242Jul., 2005
 

 
Foreign Application Priority Data   
 

Jul 29, 2004
[JP]
2004-221836

Jul 26, 2005
[JP]
2005-216228



 



  
Current U.S. Class:
  106/31.47  ; 106/31.49; 106/31.5
  
Current International Class: 
  C09D 11/02&nbsp(20060101)
  
Field of Search: 
  
  



 106/31.47,31.49,31.5 347/100
  

References Cited  [Referenced By]
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4202870
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Weber et al.

4242271
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Weber et al.

4248852
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Wakabayashi et al.

4723129
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4740796
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Endo et al.

5091009
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Nogami et al.

5123960
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Shirota et al.

5221497
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Watanabe et al.

5268459
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Gregory et al.

5395434
March 1995
Tochihara et al.

5415686
May 1995
Kurabayashi et al.

5451251
September 1995
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5482545
January 1996
Aoki et al.

5485188
January 1996
Tochihara et al.

5835116
November 1998
Sato et al.

5933164
August 1999
Sato et al.

6003987
December 1999
Yamamoto et al.

6027210
February 2000
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6186615
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6238045
May 2001
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6322209
November 2001
Sato et al.

6511534
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Mishina et al.

6698876
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Sato et al.

6712462
March 2004
Ito et al.

6779881
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Ito et al.

6790266
September 2004
Koga et al.

6976755
December 2005
Sato et al.

7087107
August 2006
Tateishi et al.

2004/0099180
May 2004
Kitayama et al.

2005/0005818
January 2005
Sato et al.

2005/0131194
June 2005
Aikawa et al.

2006/0102046
May 2006
Okamura et al.

2006/0102047
May 2006
Yoshizawa et al.

2006/0102048
May 2006
Nakamura et al.

2006/0103705
May 2006
Yoshizawa et al.

2006/0103706
May 2006
Aikawa et al.

2006/0109324
May 2006
Fujimoto et al.

2006/0119682
June 2006
Okamura et al.

2006/0119683
June 2006
Yoshizawa et al.

2006/0119685
June 2006
Yamashita et al.

2006/0124027
June 2006
Sato

2006/0137570
June 2006
Osumi et al.

2006/0146108
July 2006
Sato et al.

2006/0152569
July 2006
Jinnou et al.

2006/0156952
July 2006
Takayama et al.



 Foreign Patent Documents
 
 
 
57-44605
Sep., 1982
JP

2-233781
Sep., 1990
JP

4-233975
Aug., 1992
JP

8-73791
Mar., 1996
JP

2803134
Sep., 1998
JP

2881847
Apr., 1999
JP

11-209673
Aug., 1999
JP

2000-303009
Oct., 2000
JP

2001-288392
Oct., 2001
JP

2002-249677
Sep., 2002
JP

2002-294111
Oct., 2002
JP

2002-338853
Nov., 2002
JP

2002-338854
Nov., 2002
JP

2003-138169
May., 2003
JP

2003-238850
Aug., 2003
JP

2003-238870
Aug., 2003
JP

2003-253176
Sep., 2003
JP

2003-286423
Oct., 2003
JP

2003-321627
Nov., 2003
JP

WO 2004/104108
Dec., 2004
WO

WO 2005/033211
Apr., 2005
WO



   Primary Examiner: Klemanski; Helene


  Attorney, Agent or Firm: Fitzpatrick, Cella, Harper & Scinto



Parent Case Text



This application is a continuation of International Application No.
     PCT/JP2005/014242 filed on Jul. 28, 2005, which claims the benefit of
     Japanese Patent Application Nos. 2004-221836 filed on Jul. 29, 2004 and
     2005-216228 filed on Jul. 26, 2005.

Claims  

What is claimed is:

 1.  An ink set composed of multiple inks comprising at least: an ink jet cyan ink comprising one of a compound represented by the following general formula (1) and a compound
represented by the following general formula (2) as a coloring material;  and an ink jet yellow ink comprising at least one kind of coloring material selected from the following A group and at least one kind of coloring material selected from the
following B group;  A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula (3);  ##STR00040## wherein M represents an alkali metal
or ammonium;  R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group, provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom;  Y represents a chlorine atom, a hydroxyl group, an amino
group, or a monoalkylamino or dialkylamino group;  1 represents 0 to 2, m represents 1 to 3, and n represents 1 to 3, provided that l+m+n=3 to 4;  and positions at which substituents are present are 4- or 4'-positions;  ##STR00041## wherein M represents
a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;  ##STR00042## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently
represent 1 or 2.


 2.  An ink set composed of multiple inks comprising at least: an ink jet magenta ink comprising one of a compound represented by the following general formula (4) and a salt thereof as a coloring material;  and an ink jet yellow ink comprising
at least one kind of coloring material selected from the following A group and at least one kind of coloring material selected from the following B group;  A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142,
C.I.  Direct Yellow 86, and a compound represented by the following general formula (3);  ##STR00043## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminoalkyl or dialkyl
aminoalkyl group, or a cyano lower alkyl group;  Y represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group, which may have a substituent selected from the group consisting of a sulfonic group, a carboxyl
group, and a hydroxyl group on an alkyl group;  and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group, provided that R.sub.2, R.sub.3, R.sub.4,
R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom;  ##STR00044## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently
represent 1 or 2.


 3.  An ink set composed of multiple inks comprising at least: an ink jet cyan ink comprising one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) as a coloring
material;  an ink jet magenta ink comprising one of a compound represented by the following general formula (4) and a salt thereof as a coloring material;  and an ink jet yellow ink comprising at least one kind of coloring material selected from the
following A group and at least one kind of coloring material selected from the following B group;  A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the
following general formula (3);  ##STR00045## wherein M represents an alkali metal or ammonium;  R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group, provided that R.sub.1 and R.sub.2 are not
simultaneously a hydrogen atom;  Y represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group;  l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3, provided that l+m+n=3 to 4;  and positions at
which substituents are present are the 4- or 4'-positions;  ##STR00046## wherein M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;  ##STR00047## wherein M's each independently represent a hydrogen atom, an alkali metal, an
alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2;  ##STR00048## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl
aminoalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group;  Y represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group, which may have a substituent selected from the group consisting of a
sulfonic group, a carboxyl group, and a hydroxyl group on an alkyl group;  and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group, provided that
R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom.


 4.  An ink cartridge, comprising an ink storage portion for storing an ink set composed of multiple inks, wherein the ink set comprises the ink set according to claim 1.


 5.  An ink jet recording method, comprising ejecting ink by an ink jet method to perform recording on a recording medium, wherein the ink comprises all of the inks of the ink set according to claim 1.


 6.  A recording unit, comprising an ink storage portion for storing ink and a recording head for ejecting the ink, wherein the ink comprises all of the inks of the ink set according to claim 1.


 7.  An ink jet recording apparatus, comprising an ink storage portion for storing ink and a recording head for ejecting the ink, wherein the ink comprises all of the inks of the ink set according to claim 1. 
Description  

BACKGROUND OF THE INVENTION


1.  Field of the Invention


The present invention relates to an ink jet yellow ink, an ink set, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus each of which is capable of providing an image excellent in image storage
stability, especially environmental gas resistance and light resistance.


2.  Related Background Art


An ink jet recording method is a recording method of applying a small ink droplet to any one of recording media such as plain paper and glossy media to form an image, and had become rapidly widespread owing to a reduction in costs and improvement
in its recording rate.  With the rapid spread of digital cameras in addition to an improvement in quality of images recorded by the method, the method has been generally used as a method of outputting photographic images comparable to the silver halide
photograph.


In recent years, image quality has undergone improvement more than ever owing to, for example, extreme reduction in size of an ink droplet and an improvement of color gamut involved in the introduction of multi-color ink.  Meanwhile, there have
been growing demands for coloring materials and inks, and stricter properties have been required in respect of improvement of color developability and reliability concerning anti-clogging or ejection stability.


Meanwhile, the ink jet recording method is problematic in terms of, for example, the image storage stability of the resultant recorded article.  In general, the recorded article obtained by means of the ink jet recording method is inferior in
image storage stability to the silver halide photograph, and involves the emergence of a problem in that a coloring material on the recorded article is apt to deteriorate to cause a change in color tone of an image and the color fading of the image when
the recorded article is exposed to light, humidity, heat, an environmental gas present in the air, or the like for a long period of time.


A large number of proposals have been conventionally made in order to improve light resistance out of image storage stability.  A new coloring material has been proposed for improving the light resistance of each of yellow ink and magenta ink
each of which has particularly low light resistance out of cyan ink, the magenta ink, and the yellow ink.  C.I.  Direct Yellow 86 (see, for example, Japanese Patent Application Laid-Open No. H04-233975) and C.I Direct Yellow 173 (see, for example,
Japanese Patent Application Laid-Open No. H02-233781) have been proposed as yellow coloring materials.  A novel monoazo dye (see, for example, Japanese Patent Application Laid-Open No. H08-073791 and a novel anthrapyridone dye (see, for example, Japanese
Patent Application Laid-Open No. H11-209673) have been proposed as magenta coloring materials.


Active investigation has been made on fastness properties with respect to an environmental gas such as ozone, NO.sub.x, or SO.sub.2 present in a trace amount in the air, that is, environmental gas resistance that is of most concern out of image
storage stability in an ink jet recorded article by taking the coloring material of cyan ink that is most susceptible to the environmental gas as an example.  A novel phthalocyanine dye has been proposed as an example of the coloring material (see, for
example, Japanese Patent Applications Laid-Open No. 2002-249677 and No. 2000-303009).


The use of a specific coloring material having high fastness properties for each color has been proposed for improving the light resistance of an ink set in consideration of a color balance between inks of respective colors (see, for example,
Japanese Patent Applications Laid-Open No. 2001-288392, No. 2002-338853, No. 2002-294111, and No. 2003-138169).  There has been also proposed a method of improving ozone resistance (see, for example, Japanese Patent Applications Laid-Open No. 2003-238850
and No. 2003-286423).


However, no technique in consideration of a color fading balance has been conventionally established in terms of a correlation between yellow ink and any other color ink.


SUMMARY OF THE INVENTION


Evaluation on resistance to only an ozone gas as an environmental gas has been conventionally made.  However, the inventors of the present invention have made studies to find that evaluation only on an ozone gas may not correspond to the image
storage stability when a recorded article having an actual image such as a photograph printed thereon is stored.  This is because a recorded article having an image such as a photograph printed thereon is often stored in an environment containing a large
amount of acid gases such as NO.sub.x and SO.sub.2 as well as an ozone gas such as a room.  The inventors have found that a recorded article having an actual image such as a photograph printed thereon can be evaluated for image storage stability by
performing evaluation on image storage stability in an environment containing a large amount of acid gases such as NO.sub.x and SO.sub.2 as well as an ozone gas.  As a result, the inventors of the present invention have acknowledged that ink capable of
improving the image storage stability of a recorded article having an image such as a photograph printed thereon in an environment containing a large amount of acid gases such as NO.sub.x and SO.sub.2 as well as an ozone gas is needed.


The inventors of the present invention have made studies to find the following.  That is, for example, when a recorded article obtained by means of conventional ink such as yellow ink, magenta ink, or cyan ink is exposed to an environmental gas
for a long time period, the entire recorded article yellows to thereby make the deterioration of an image remarkable.  This is because, for example, (1) the yellow ink, the magenta ink, and the cyan ink can be arranged into the cyan ink, the magenta ink,
and the yellow ink in order of decreasing degree of color fading in each color, (2) the color of the coloring material of the cyan ink changes to a yellowish color when the coloring material deteriorates, and (3) a recording medium yellows owing to
NO.sub.x or the like in the environmental gas.


Accordingly, an effective measure to improve environmental gas resistance involves uniformizing a color fading balance among yellow ink, magenta ink, and cyan ink in a recorded article while taking a change in color of the coloring material of
the cyan ink and the yellowing of a recording medium in consideration, to thereby maintain a color balance even when color fading occurs.  In other words, it is important to satisfy a correlation between yellow ink and at least one kind of other ink.


The inventors of the present invention have made further studies to find that an acceleration test using an environmental gas present in the atmosphere of a room environment is essential to the case where an acceleration test in which a state
where a recorded article having an image such as a photograph printed thereon is presented in a room, the state causing a problem in terms of image storage stability, is simulated with improved accuracy is performed.  Therefore, it is necessary to
perform an acceleration test in a mixed gas system taking into considerations an influence of ant acid gas such as NO.sub.x present at a higher concentration than that of ozone in the atmosphere of a general room environment rather than an influence of
an ozone gas alone that has been conventionally considered to have the largest influence on an image obtained by means of an ink jet recording method.  Therefore, the inventors of the present invention have concluded that the improvement of image storage
stability with respect to a mixed gas containing three kinds of gases, that is, an ozone gas, and NO.sub.x and SO.sub.2 as acid gases, as environmental gas resistance is essential to the improvement of image storage stability in a state where a recorded
article is presented in a room.


Therefore, an object of the present invention is to provide an ink jet yellow ink to be used in combination with an ink jet cyan ink containing a specific coloring material excellent in light resistance and environmental gas resistance with a
color fading balance with respect to light and an environmental gas between the yellow ink and the cyan ink uniformized.


Another object of the present invention is to provide an ink jet yellow ink to be used in combination with an ink jet magenta ink containing a specific coloring material excellent in light resistance and environmental gas resistance with a color
fading balance with respect to light and an environmental gas between the yellow ink and the magenta ink-uniformized.


Another object of the present invention is to provide an ink jet yellow ink to be used in combination with an ink jet magenta ink and an ink jet cyan ink each containing a specific coloring material with a color fading balance with respect to
light and an environmental gas among the three color inks uniformized.


Another object of the present invention is to provide an ink set containing at least an ink jet magenta ink, an ink jet cyan ink, and an ink jet yellow ink each containing a specific coloring material with a color fading balance with respect to
light and an environmental gas among the three color inks uniformized.


Another object of the present invention is to provide an ink jet recording method with which an image to be formed on a recording medium by means of the above ink jet ink that does not undergo color fading owing to light and an environmental gas
can be obtained.


Another object of the present invention is to provide an ink cartridge, a recording unit, and an ink jet recording apparatus each using the above ink jet ink.


The above objects are achieved by the present invention described below.  That is, according to one aspect of the present invention, there is provided an ink jet yellow ink to be used for forming an image together with a cyan ink comprising one
of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) as a coloring material, the ink jet yellow ink comprising: at least one kind of coloring material selected from the following A
group; and at least one kind of coloring material selected from the following B group; A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following
general formula (3);


 ##STR00001## wherein M represents an alkali metal or ammonium; R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group (provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom); Y
represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group; l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3 (provided that l+m+n=3 to 4); and positions at which substituent are present are
the 4- or 4'-positions;


 ##STR00002## wherein M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;


 ##STR00003## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2.


According to another aspect of the present invention, there is provided an ink jet yellow ink to be used for forming an image together with a magenta ink comprising one of a compound represented by the following general formula (4) or a salt
thereof as a coloring material, the ink jet yellow ink comprising: at least one kind of coloring material selected from the following A group; and at least one kind of coloring material selected from the following B group; A group: C.I.  Direct Yellow
132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula: (3);


 ##STR00004## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminoalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group; Y represents a chlorine atom, a hydroxyl
group, an amino group, or a monoalkylamino or dialkylamino group which may have a substituent selected from the group consisting of a sulfonic group, a carboxylgroup, and a hydroxyl group on an alkyl group; and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom);


 ##STR00005## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2.


According to another aspect of the present invention, there is provided an ink jet yellow ink to be used for forming an image together with an ink jet cyan ink comprising one of a compound represented by the following general formula (1) and a
compound represented by the following general formula (2) as a coloring material and with an ink jet magenta ink comprising at least one of a compound represented by the following general formula (4) or a salt thereof as a coloring material, the ink jet
yellow ink comprising: at least one kind of coloring material selected from the following A group; and at least one kind of coloring material selected from the following B group; A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I. 
Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula (3);


 ##STR00006## wherein M represents an alkali metal or ammonium; R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group (provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom); Y
represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group; l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3 (provided that l+m+n=3 to 4); and positions at which substituents are present are
the 4- or 4'-positions;


 ##STR00007## wherein M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;


 ##STR00008## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2;


 ##STR00009## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminoalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group; Y represents a chlorine atom, a hydroxyl
group, an amino group, or a monoalkylamino or dialkylamino group (which may have a substituent selected from the group consisting of a sulfonic group, a carboxyl group, and a hydroxyl group on an alkyl group); and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom).


According to another aspect of the present invention, there is provided an ink set composed of multiple inks comprising at least: an ink jet cyan ink comprising one of a compound represented by the following general formula (1) and a compound
represented by the following general formula (2) as a coloring material; and an ink jet yellow ink comprising at least one kind of coloring material selected from the following A group and at least one kind of coloring material selected from the
following B group; A group: C.I.  Direct.  Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula (3);


 ##STR00010## wherein M represents an alkali metal or ammonium; R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group (provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom); Y
represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group; l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3 (provided that l+m+n=3 to 4); and positions at which substituents are present are
4- or 4'-positions;


 ##STR00011## wherein M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;


 ##STR00012## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2.


According to another aspect of the present invention, there is provided an ink set composed of multiple inks comprising at least an ink jet magenta ink comprising one of a compound represented by the following general formula (4) or a salt
thereof as a coloring material; and an ink jet yellow ink comprising at least one kind of coloring material selected from the following A group and at least one kind of coloring material selected from the following B group; A group: C.I.  Direct Yellow
132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula (3);


 ##STR00013## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminoalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group; Y represents a chlorine atom, a hydroxyl
group, an amino group, or a monoalkylamino or dialkylamino group (which may have a substituent selected from the group consisting of a sulfonic group, a carboxyl group, and a hydroxyl group on an alkyl group); and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom);


 ##STR00014## wherein M's each independently represents a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2.


According to another aspect of the present invention, there is provided an ink set composed of multiple inks comprising at least: an ink jet cyan ink comprising one of a compound represented by the following general formula (1) and a compound
represented by the following general formula (2) as a coloring material; an ink jet magenta ink comprising one of a compound represented by the following general formula (4) or a salt thereof as a coloring material; and an ink jet yellow ink comprising
at least one kind of coloring material selected from the following A group and at least one kind of coloring material selected from the following B group; A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I. Direct Yellow 86, and a compound, represented by the following general formula (3);


 ##STR00015## wherein M represents an alkali metal or ammonium; R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group (provided that R.sub.1 and R.sub.2 are not simultaneously a hydrogen atom); Y
represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group; l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3 (provided that l+m+n=3 to 4); and positions at which substituents are present are
the 4- or 4'-positions;


 ##STR00016## wherein M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium;


 ##STR00017## wherein M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2;


 ##STR00018## wherein R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminioalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group; Y represents a chlorine atom, a hydroxyl
group, an amino group, or a monoalkylamino or dialkylamino group (which may have a substituent selected from the group consisting of a sulfonic group, a carboxyl group, and a hydroxyl group on an alkyl group); and R.sub.2, R.sub.3, R.sub.4, R.sub.5, and
R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom).


According to another aspect of the present invention, there is provided an ink jet recording method, including ejecting an ink by an ink jet method to perform recording on a recording medium, in which the ink is the ink jet yellow ink having the
above constitution.


According to another aspect of the present invention, there is provided an ink cartridge, including an ink storage portion for storing ink, in which the ink is the ink jet yellow ink having the above constitution.


According to another aspect of the present invention, there is provided an ink cartridge, including an ink storage portion for storing an ink set composed of multiple inks, in which the ink set is the ink set having the above constitution.


According to another aspect of the present invention, there is provided a recording unit, including an ink storage portion for storing ink and a recording head for ejecting the ink, in which the ink is the ink jet yellow ink having the above
constitution.


According to another aspect of the present invention, there is provided an ink jet recording apparatus, including an ink storage portion for storing ink and a recording head for ejecting the ink, in which the ink is the ink jet ink having the
above constitution.


According to the present invention, there can be provided an ink jet yellow ink to be used in combination with an ink jet cyan ink containing a specific coloring material excellent in light resistance and environmental gas resistance with a color
fading balance with respect to light and an environmental gas between the yellow ink and the cyan ink uniformized.


According to another aspect of the present invention, there can be provided an ink jet yellow ink to be used in combination with an ink jet magenta ink containing a specific coloring material excellent in light resistance and environmental gas
resistance with a color fading balance with respect to light and an environmental gas between the yellow ink and the magenta ink uniformized.


According to another aspect of the present invention, there can be provided an ink jet yellow ink to be used in combination with an ink jet magenta ink and an ink jet cyan ink each containing a specific coloring material with a color fading
balance with respect to light and an environmental gas among the three color inks uniformized.


According to another aspect of the present invention, there can be provided an ink set containing at least an ink jet magenta ink, an ink jet cyan ink, and an ink jet yellow ink each containing a specific coloring material with a color fading
balance with respect to light and an environmental gas among the three color inks uniformized.


According to another aspect of the present invention, there can be provided an ink jet recording method with which an image to be formed on a recording medium by means of the above ink jet ink that does not undergo color fading owing to light and
an environmental gas can be obtained.


According to another aspect of the present invention, there can be provided an ink cartridge, a recording unit, and an ink jet recording apparatus each using the above ink jet ink. 

BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 shows an image of the deterioration of an image density with time;


FIG. 2 is a perspective view of a recording apparatus;


FIG. 3 is a perspective view of a mechanism portion of the recording apparatus;


FIG. 4 is a sectional view of the recording apparatus;


FIG. 5 is a perspective view showing a state where an ink tank is mounted on a head cartridge;


FIG. 6 is an exploded perspective view of the head cartridge;


FIG. 7 is a front view showing a recording element substrate in the head cartridge;


FIG. 8 is an exploded view of a recording head; and


FIG. 9 is an exploded view of a recording head.


DESCRIPTION OF THE PREFERRED EMBODIMENTS


Hereinafter, the present invention will be described in more detail by way of preferred embodiments.


In the present invention, when a compound is a salt, the salt is dissociated to ions in ink, but this state is represented by using the phrase "contains a salt" for convenience.  Further, ink jet ink may hereinafter be simply referred to as the
"ink".


(Ink)


Hereinafter, components constituting the ink according to the present invention and the like will be described in detail.


(Coloring Material of Yellow Ink)


As described above, the yellow ink according to the present invention is requested to have the degree of color fading with respect to an environmental gas and light comparable to that of each of a cyan ink and a magenta ink.  In the present
invention, a coloring material is selected in such a manner that a yellow ink has high light resistance and shows environmental gas resistance comparable to that of each of a magenta ink and a cyan ink.  Such coloring materials as listed above to be used
as coloring materials of yellow inks show the same light resistance, but are different from each other in environmental gas resistance.  To be specific, a coloring material belonging to the A group to be used alone shows higher environmental gas
resistance than that of each of a magenta ink and a cyan ink to be described later, while a coloring material belonging to the B group to be used alone shows lower environmental gas resistance than that of a cyan ink to be described later.  Accordingly,
environmental gas resistance comparable to that of each of a magenta ink and a cyan ink to be described later can be obtained by: selecting at least one kind of coloring material from the A group and at least one kind of coloring material from the B
group; and mixing the selected coloring materials at a preferable ratio.  Thus, a yellow ink excellent in color fading balance can be obtained.


The yellow ink according to the present invention must be prepared by using in combination at least one kind of coloring material selected from the compounds described in the A group and at least one kind of coloring material selected from the
compounds described in the B group.  A group: C.I.  Direct Yellow 132 and C.I.  Direct Yellow 173 B group: C.I.  Direct Yellow 142, C.I.  Direct Yellow 86, and a compound represented by the following general formula (3)


 ##STR00019## (In the general formula (3), M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or an ammonium ion, and n's each independently represent 1 or 2.)


Specific examples of the coloring material represented by the general formula (3) include compounds having the structures shown in Table 1 below.  Of course, the present invention is not limited to them.  In Table 1, for convenience, the
substitution position of a sulfonic group is represented as a position in an A ring or a B ring as shown in the following general formula (5).  The substitution position of a sulfonic group is as defined in the following general formula (5).


 ##STR00020## (In the general formula (5), M's each independently represent a hydrogen atom, an alkali metal, an alkali earth metal, a cation of organic amine or ammonium ion, and n's each independently represent 1 for 2.)


 TABLE-US-00001 TABLE 1 Position of substituent A ring B ring Exemplified Compound Y1 2 4 Y2 4 4 Y3 2 4, 6 Y4 4, 6 4


A preferable specific example of the coloring material represented by the general formula (5) includes Exemplified Compound Y1 below.  Of course, the present invention is not limited thereto.


 ##STR00021##


The content (mass %) of the coloring material in the yellow ink is preferably 1.0 mass % or more and 10.0 mass % or less, or more preferably 1.5 mass % or more and 6.0 mass % or less with respect to the total mass of the ink.  A content of less
than 1.0 mass % may not sufficiently provide the effects of the present invention such as a color fading balance, while a content in excess of 10.0 mass % may not provide ink jet properties such as anti-sticking property.  In addition, a ratio (%)
between the content (mass %) of the coloring material belonging to the A group and the content (mass %) of the coloring material belonging to the B group in the yellow ink (the content (mass %) of the coloring material belonging to the A group: the
content (mass %) of the coloring material belonging to the B group) is preferably 1:10 to 10:1.  This is because a ratio in the above range effectively provides an excellent color fading balance as one of the effects of the present invention.


(Coloring Material of Magenta Ink)


The magenta ink according to the present invention is requested to have high light resistance and to show environmental gas resistance comparable to that of the above yellow ink.  Therefore, a compound represented by the following general formula
(4) or a salt thereof is preferably used as a coloring material of the magenta ink.  Each of the coloring materials to be used as a coloring material of the magenta ink shows high light resistance, but its environmental gas resistance to an ozone gas
alone in an environmental gas is different from its environmental gas resistance to a mixed gas containing an ozone gas and an acid gas such as NO.sub.x or SO.sub.2.  To be specific, each coloring material shows low resistance to an ozone gas alone, but
shows high resistance to a mixed gas containing an ozone gas and an acid gas.


 ##STR00022## (In the general formula (4): R.sub.1 represents a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a monoalkyl aminoalkyl or dialkyl aminoalkyl group, or a cyano lower alkyl group; Y represents a
chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group (which may have a substituent selected from the group consisting of a sulfonic group, a carboxyl group, and a hydroxyl group on an alkyl group); and R.sub.2,
R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are not simultaneously a hydrogen atom).)


Preferable specific examples of the compound represented by the general formula (4) include Exemplified Compounds M1 to M7 below.  Of course, the present invention is not limited thereto.


Exemplified Compounds M1 to M7


 ##STR00023## ##STR00024##


The content (mass %) of the coloring material in the magenta ink is preferably 1.0 mass % or more and 10.0 mass % or less, or more preferably 1.5 mass % or more and 6.0 mass % or less with respect to the total mass of the ink.  A content of less
than 1.0 mass % may not sufficiently provide the effects of the present invention such as a color fading balance, while a content in excess of 10.0 mass % may not provide ink jet properties such as anti-sticking property.


(Coloring Material of Cyan Ink)


The cyan ink according to the present invention is requested to have high environmental gas resistance comparable to that of each of the yellow ink and the magenta ink.  Therefore, a compound represented by the following general formula (1) or a
compound represented by the following general formula (2) is preferably used as a coloring material of the cyan ink.  It should be noted that only one kind selected from the compounds each represented by the general formula (1) or (2) may be used, or two
or more kinds selected therefrom may be used in combination.


 ##STR00025## (In the general formula (1): M represents an alkali metal or ammonium; R.sub.1 and R.sub.2 each independently represent a hydrogen atom, a sulfonic group, or a carboxyl group (provided that R.sub.1 and R.sub.2 are not simultaneously
a hydrogen atom); Y represents a chlorine atom, a hydroxyl group, an amino group, or a monoalkylamino or dialkylamino group; l represents 0 to 2, m represents 1 to 3, and n represents 1 to 3 (provided that l+m+n=3 to 4); and positions at which
substituent are present are the 4- or 4'-positions.)


The coloring material to be used in the present invention is a phthalocyanine derivative prepared by selectively introducing an unsubstituted sulfamoyl group (--SO.sub.2NH.sub.2) or a substituted sulfamoyl group (a group represented by the
following general formula (6)) to each of only 4- and 4'-positions in the general formula (1).  The inventors of the present invention have found that a recorded article obtained by means of ink containing such compound is extremely excellent in
environmental gas resistance.


A phthalocyanine compound prepared by reacting a 4-sulfophthalic acid derivative, or a 4-sulfophthalic acid derivative and phthalic acid (anhydride) derivative, in the presence of a metal compound is used as a raw material for synthesizing a
compound represented by the general formulae (1) or a salt thereof.  A sulfonic group in the phthalocyanine compound is transformed into a chlorosulfonic group, and then an amination agent is allowed to react with the resultant in the presence of an
organic amine to synthesize the compound or the salt thereof.


 ##STR00026##


Preferable specific examples of the substituted sulfamoyl group represented by the general formula (6) are shown below.  Of course, the substituted sulfamoyl group used in the present invention is not limited thereto.  The substituted sulfamoyl
group represented by the general formula (6) is shown in the form of a free acid.  Of those, a compound substituted by Exemplified Substituent 1 is most preferable because of its balance between color developability and environmental gas resistance.


Exemplified Substituents 1 to 7


 ##STR00027## ##STR00028##


 ##STR00029## (In the general formula (2), M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium.)


The content (mass %) of the coloring material in the cyan ink is preferably 1.0 mass % or more and 10.0 mass % or less, or more preferably 1.5 mass % or more and 6.0 mass % or less with respect to the total mass of the ink.  A content of less
than 1.0 mass % may not sufficiently provide the effects of the present invention such as a color fading balance, while a content in excess of 10.0 mass % may not provide ink jet properties such as anti-sticking property.


(Coloring Materials of Other Inks)


Each of the yellow ink according to the present invention, and the magenta ink and the cyan ink to be used in combination with the yellow ink may contain another coloring material as well as the above coloring material.  Specific examples of the
other coloring material are shown below.  Of course, the present invention is not limited thereto.


The content (mass %) of the other coloring material to be incorporated into each of the yellow ink according to the present invention, and the magenta ink and the cyan ink to be used in combination with the yellow ink is as follows.


For the yellow ink, a ratio of the content of a coloring material except those belonging to the A and B groups to the total content of the coloring materials is preferably less than 20%.  For the magenta ink, a ratio of the content of a coloring
material except the compound represented by the general formula (4) or the salt thereof to the total content of the coloring materials is preferably less than 20%.  For the cyan ink, a ratio of the content of a coloring material except the compound
represented by the general formula (1) or the compound represented by the general formula (2) to the total content of the coloring materials is preferably less than 20%.  The above contents are preferable because a color fading balance as one of the
effects of the present invention becomes excellent.


The yellow ink according to the present invention may be used in combination with another ink as well as the magenta ink and the cyan ink described above.  Specific examples of a coloring material to be incorporated into ink that can be used in
combination with the yellow ink according to the present invention are shown below.  Of course, the present invention is not limited thereto.


(Yellow Coloring Material) C.I.  Direct Yellow: 8, 11, 12, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110, 132, and 173 C.I.  Acid Yellow: 1, 3, 7, 11, 17, 23, 25, 29, 36, 38, 40, 42, 44, 76, 98, and 99 C.I.  Pigment Yellow: 1, 2,
3, 12, 13, 14, 15, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 128, 138, and 180


(Magenta Coloring Material) C.I.  Direct Red: 2, 4, 9, 11, 20, 23, 24, 31, 39, 46, 62, 75, 79, 80, 83, 89, 95, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, and 230 C.I.  Acid Red: 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 42, 51, 52, 80, 83, 87,
89, 92, 106, 114, 115, 133, 134, 145, 158, 198, 249, 265, and 289 C.I.  Food Red: 87, 92, and 94 C.I.  Direct Violet: 107 C.I.  Pigment Red: 2, 5, 7, 12, 48:2, 48:4, 57:1, 112, 122, 123, 168, 184, and 202


(Cyan Coloring Material) C.I.  Direct Blue: 1, 15, 22, 25, 41, 76, 77, 80, 86, 90, 98, 106, 108, 120, 158, 163, 168, 199, 226, and 307.  C.I.  Acid Blue: 1, 7, 9, 15, 22, 23, 25, 29, 40, 43, 59, 62, 74, 78, 80, 90, 100, 102, 104, 112, 117, 127,
138, 158, 161, 203, 204, 221, and 244 C.I.  Pigment Blue: 1, 2, 3, 15, 15:2, 15:3, 15:4, 16, 22, and 60 (Coloring Materials Having Other Color Tones)


The yellow ink according to the present invention may be used in combination with so-called special color inks such as black, red, green, and blue inks as required as well as the above inks.  Examples of coloring materials that can be
incorporated into those inks are shown below.  Of course, the present invention is not limited thereto.  C.I.  Acid Orange: 7, 8, 10, 12, 24, 33, 56, 67, 74, 88, 94, 116, and 142 C.I.  Acid Red: 11, 114, 266, and 374 C.I.  Direct Orange: 26, 29, 34, 39,
57, 102, and 118 C.I.  Food Orange: 3 C.I.  Reactive Orange: 1, 4, 5, 7, 12, 13, 14, 15, 16, 20, 29, 30, 84, and 107 C.I.  Disperse Orange: 1, 3, 11, 13, 20, 25, 29, 30, 31, 32, 47, 55, and 56 C.I.  Pigment Orange: 43 C.I.  Pigment Red: 122, 170, 177,
194, 209, and 224 C.I.  Acid Green: 1, 3, 5, 6, 9, 12, 15, 16, 19, 21, 25, 28, 81, and 84 C.I.  Direct Green: 26, 59, and 67 C.I.  Food Green: 3 C.I.  Reactive Green: 5, 6, 12, 19, and 21 C.I.  Disperse Green: 6 and 9 C.I.  Pigment Green: 7 and 36 C.I. 
Acid Blue: 62, 80, 83, 90, 104, 112, 113, 142, 203, 204, 221, and 244 C.I.  Reactive Blue: 49 C.I.  Acid Violet: 17, 19, 48, 49, 54, and 129 C.I.  Direct Violet: 9, 35, 47, 51, 66, 93, 95, and 99 C.I.  Reactive Violet: 1, 2, 4, 5, 6, 8, 9, 22, 34, and 36
C.I.  Disperse Violet: 1, 4, 8, 23, 26, 28, 31, 33, 35, 38, 48, and 56 C.I.  Pigment Blue: 15:6 C.I.  Pigment Violet: 19, 23, and 37 C.I.  Direct Black: 17, 19, 22, 31, 32, 51, 62, 71, 74, 112, 113, 154, 168, and 195 C.I.  Acid Black: 2, 48, 51, 52, 110,
115, and 156 C.I.  Food Black: 1 and 2 Carbon black


(Black Ink)


The yellow ink according to the present invention can be used in combination with another ink as well as the magenta ink and the cyan ink described above.  In the present invention, in particular, the yellow ink is preferably used in combination
with black ink.  This is because the use of the black ink allows a black image having a high image density and an excellent hue to be formed.


The black ink preferably contains at least one coloring material selected from: a compound represented by the following general formula (7) or a salt thereof; a compound represented by the following general formula (8) or a salt thereof; and a
condensed dye of a compound represented by the following general formula (9) and a compound represented by the following general formula (10).  This is because those coloring materials are excellent in fastness properties, hue, and image density.


 ##STR00030## (In the general formula (7), R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently represent a hydrogen atom; a hydroxyl group; an amino group; a carboxyl group; a sulfonic group; an alkyl group having 1 to 4 carbon atoms; an
alkoxy group having 1 to 4 carbon atoms; an alkoxy group substituted by a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic group, or a carboxyl group; an alkoxy group having 1 to 4 carbon atoms which may be additionally substituted
by a carboxyl group or a sulfonic group; or an amino group substituted by a phenyl group, an alkyl group, or an acyl group, and n represents 0 or 1.)


 ##STR00031## (In the general formula (8), R.sub.1 and R.sub.2 each independently represent a hydrogen atom; a hydroxyl group; an amino group; a carboxyl group; a sulfonic group; an alkyl group having 1 to 4 carbon atoms; or an alkoxy group
having 1 to 4 carbon atoms, R.sub.3 and R.sub.4 each independently represent: a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms; a hydroxyl group; an alkyl group having 1 to 4 carbon atoms which may be
substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic group, or a carboxyl group; or
an amino group substituted by an alkyl group or an acyl group, and n represents 0 or 1.)


 ##STR00032## (In the general formula (9), M represents a hydrogen atom or an alkali metal atom.)


 ##STR00033## (In the general formula (10), R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent a hydrogen atom; a halogen atom; a hydroxyl group; a sulfonic group; a carboxyl group; an alkyl group having 1 to 4 carbon
atoms; or an alkoxy group having 1 to 4 carbon atoms.)


(Red Ink, Blue Ink, and Green Ink)


The yellow ink according to the present invention can be used in combination with another ink as well as the magenta ink and the cyan ink described above.  In the present invention, the yellow ink is preferably used in combination with red ink,
blue ink, or green ink.  This is because the combined use of the yellow ink and the red, blue, or green ink allows a vivid image having a wide color gamut to be formed.


The red ink preferably contains at least C.I.  Food Red 3 as a coloring material.  This is because the coloring material is excellent in color developability, and the use thereof allows a vivid image having a wide color gamut to be formed.


The blue ink preferably contains at least C.I.  Direct Blue 199 as a coloring material.  This is because the coloring material is excellent in color developability, and the use thereof allows a vivid image having a wide color gamut to be formed.


The green ink preferably contains at least a compound represented by the following general formula (11) or a salt thereof and a compound represented by the following general formula (12) or a salt thereof as coloring materials.  This is because
those coloring materials are excellent in color developability, and the use thereof allows a vivid image having a wide color gamut to be formed.


 ##STR00034## (In the general formula (11): R.sub.1 and R.sub.2 each independently represent a substituted or unsubstituted alkyl, aryl, or arylalkyl group, or a hydrogen atom; R.sub.3 and R.sub.5 each independently represent a carboxyl group or
a salt thereof, a sulfonic group or a salt thereof, a phosphate group or a salt thereof, or an alkyl group substituted by any one of these groups; R.sub.4 and R.sub.6 each independently represent a group except those defined for R.sub.3 and R.sub.5; p
and r each independently represent an integer of 1 to 5; q and s each independently represent an integer of 0 to 4; and p+q.ltoreq.5 and r+s.ltoreq.5.)


 ##STR00035## (In the general formula (12): M represents an alkali metal (such as Li, Na, K, Rb, Cs, or Fr) or ammonium; R.sub.7 represents OH, COOM, or R.sub.8COOM: (where R.sub.8 represents an alkyl group having 4 to 9 carbon atoms and M
represents an alkali metal or ammonium); and x, y, and z each independently represent 0, 1, 2, 3, or 4.)


(Aqueous Medium)


Water or an aqueous medium as a mixed solvent of water and various water-soluble organic solvents can be used for each ink constituting the ink set of the present invention.


The water-soluble organic solvents are not particularly limited as long as they are water-soluble, and examples thereof include an alcohol, polyhydric alcohol, polyglycol, glycol ether, a nitrogen-containing polar solvent, and a sulfur-containing
polar solvent.  Examples of a water-soluble organic solvent that can be used for the ink of the present invention are shown below, but the present invention is not limited to these water-soluble organic solvents.  Specific examples of the water-soluble
organic solvents include: alkyl alcohols each having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; amides such as dimethylformamide and
dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene glycols in each of which an alkylene group
has 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexane triol, thio diglycol, hexylene glycol, and diethylene glycol; lower alkyl ether acetates such as polyethylene glycol monomethyl ether
acetate; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether; polyhydric alcohols such as trimethylolpropane and
trimethylolethane; glycerin; N-methyl-2-pyrrolidone; 2-pyrrolidone; and 1,3-dimethyl-2-imidazolidinone.  Of course, the present invention is not limited thereto.  Each of the water-soluble organic solvents may be used alone, or two or more of them may be
used in combination.


The total content of those water-soluble organic solvents is preferably 5 mass % to 90 mass %, or more preferably 10 mass % to 50 mass % with respect to the total mass of the ink.  A content of less than 5 mass % may cause the deterioration of
reliability such as ejection property when the ink of the present invention is used as ink jet ink, while a content in excess of 90 mass % may cause insufficient supply of ink due to an increase in viscosity of the ink.


In addition, deionized water (ion-exchanged) is desirably used as water.  The water content is preferably 10 mass % to 90 mass % with respect to the total mass of the ink.


(Other Additive)


In the present invention, various additives such as a surfactant, a pH adjustor, a rust inhibitor, an antiseptic, a mildewproofing agent, an antioxidant, an antireducing agent, an evaporation accelerator, a chelating agent, and a water-soluble
polymer may be incorporated into each ink constituting the ink set as required.


(Ink Set)


The term "ink set" as used herein refers to a state where the yellow ink constituting the present invention is used in combination with the specific cyan and magenta inks constituting the present invention.  For example, the term includes, of
course, an ink tank itself having multiple ink tank portions integrated with each other.  Furthermore, the term includes a state where multiple ink tanks different from each other are used together and a state where these ink tanks are integrated into a
head portion.


(Recording Medium)


Any recording medium can be used for forming an image by means of the ink of the present invention as long as recording is performed by applying the ink to the recording medium.


The present invention is applicable to a recording medium in which a coloring material such as a dye or a pigment is adsorbed to a fine particle forming a porous structure in an ink-receiving layer and an image is formed from at least the fine
particle having adsorbed thereto the coloring material, and the present invention is particularly suitable for the case where an ink-jet method is used.  Such ink jet recording medium is preferably of a so-called absorption type in which ink is absorbed
by a gap formed in an ink-receiving layer on a support.


An absorption type ink-receiving layer is constituted as a porous layer mainly composed of a fine particle and containing a binder and any other additive as required.  Specific examples of the fine particle include: inorganic pigments such as
silica, clay, talc, calcium carbonate, kaolin, aluminum oxide (for example, alumina or alumina hydrate), diatomaceous earth, titanium oxide, hydrotalcite, and zinc oxide; and organic pigments such as a urea formalin resin, an ethylene resin, and a
styrene resin.  One or more kinds of them are used.  Examples of a binder that is suitably used include a water-soluble polymer and a latex.  Examples of an available binder include: polyvinyl alcohol or a denatured product thereof; starch or a denatured
product thereof; gelatin or a denatured product thereof; gun arabic; cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, and hydroxyproylmethylcellulose; vinyl-based copolymer latexes such as an SBR latex, an NBR latex, a methyl
methacrylate-butadiene copolymer latex, a functional group-denatured polymer latex, and an ethylene-vinyl acetate copolymer; polyvinyl pyrrolidone; maleic anhydride or a copolymer thereof; and an acrylate copolymer.  Two or more kinds of them can be used
in combination as required.  In addition, an additive may be used, and examples of an additive to be used as required include a dispersant, a thickener, a pH adjustor, a lubricant, a fluidity denaturing agent, a surfactant, a defoaming agent, a releasing
agent, a fluorescent bleach, a UV absorber, and an antioxidant.


In particular, a recording medium having formed thereon an ink-receiving layer mainly composed of fine particles having an average particle size of 1 .mu.m or less is preferably used in the present invention.  Particularly preferable examples of
the fine particles include silica fine particles and aluminum oxide fine particles.  Preferable silica fine particles are silica fine particles typified by colloidal silica.  Colloidal silica, which itself is available from the market, is particularly
preferably that described in JP 2803134 B or JP 2881847 B. Preferable aluminum oxide fine particles are alumina hydrate fine particles and the like.  An alumina hydrate represented by the following general formula can be exemplified as one example of
such alumina hydrate fine particles.  AlO.sub.3-n(OH).sub.2n.mH.sub.2O (In the formula; n represents an integer of 1, 2, or 3, and m represents a value of 0 to 10, or preferably 0 to 5; provided, however, that m and n are not simultaneously 0.  m may be
or may not be an integer because mH.sub.2O also represents an aqueous phase that can desorb and is not involved in the formation of an mH.sub.2O crystal lattice in many cases.  In addition, heating such kind of material may cause m to reach 0.)


An alumina hydrate can be produced by means of a conventionally known method such as: the hydrolysis of aluminum alkoxide or sodium aluminate described in U.S.  Pat.  No. 4,242,271 or U.S.  Pat.  No. 4,202,870; or a method involving adding an
aqueous solution of sodium sulfate, aluminum chloride, or the like to an aqueous solution of sodium aluminate or the like to perform neutralization described in JP 57-44605 B.


The recording medium preferably has a support for supporting the above-described ink-receiving layer.  Any support can be used without any particular limitation as long as its ink-receiving layer can be formed of the above-described porous fine
particles and the support provides rigidity such that the support can be conveyed by a conveying mechanism of an ink jet printer or the like.  Specific examples thereof include: a paper support formed of a pulp raw material mainly composed of natural
cellulose fibers; a plastic support composed of a material such as polyester (for example, polyethylene terephthalate), cellulose triacetate, polycarbonate, polyvinyl chloride, polypropylene, or polyimide; resin-coated paper (for example, RC paper)
having, on at least one side of base paper, a polyolefin resin coating layer added with a white pigment or the like.


(Ink Jet Recording Method)


The ink according to the present invention is particularly suitably used for an ink jet recording method including the step of ejecting the ink by an ink jet method.  Examples of the ink jet recording method include a recording method involving
applying mechanical energy to ink to eject the ink and a recording method involving applying thermal energy to ink to eject the ink.  An ink jet recording method involving the use of thermal energy is particularly preferably used in the present
invention.


(Ink Cartridge)


An example of an ink cartridge suitable for performing recording by means of the ink according to the present invention includes an ink cartridge including an ink storage portion for storing the ink.


In the present invention, an ink cartridge having a substantially equal difference in amount of evaporation between any two liquid chambers for inks constituting an ink set can be preferably used in the present invention.  The phrase "a
substantially equal difference in amount of evaporation between any two liquid chambers for inks constituting an ink set" refers to a state where a difference in evaporation rate between any two liquid chambers becomes about 1% or less, for example, when
the evaporation rate of water incorporated into each of the liquid chambers is measured.


FIG. 8 is an exploded view of a recording head that can be used for the present invention.  The recording head shown in FIG. 8 is integrated with an ink tank.  A recording head 1001 is supported by and fixed to carriage positioning means mounted
on an ink jet recording apparatus main body and an electrical contact, and is detachable to a carriage.  The recording head is replaced when mounted ink is consumed.


The recording head 1001, which is intended for the ejection of ink, is constituted by: a recording element substrate 1100 on which ink supply orifices are formed in parallel; an electric wiring tape 1300 for forming an electrical signal path
through which an electrical signal for ejecting ink is applied; an ink supply/hold member 1400 formed by molding a resin; an ink absorbent 1500 for generating a negative pressure for holding the ink; and a cap member 1600.


The ink supply/hold member 1400 has a space for holding the absorbent 1500 for generating a negative pressure for holding cyan, magenta, and yellow inks in the absorbent to provide a function as an ink tank, and forms an independent ink flow path
for introducing ink to the ink supply orifices of the recording element substrate 1100 to provide an ink supply function.  An ink supply orifice 1200 for supplying ink to the recording element substrate 1100 is formed at a downstream portion of the ink
flow path, and the recording element substrate 1100 is fixed to the ink supply/hold member 1400 in such a manner that the ink supply orifices of the recording element substrate 1100 are in communication with the ink supply orifice 1200 of the ink
supply/hold member 1400.  In addition, the rear surface of part of the electric wiring tape 1300 is fixed to the plane around the vicinity of the ink supply orifice 1200.  The cap member 1600 is welded of an upper opening portion of the ink supply/hold
member 1400 to close the space inside the ink supply/hold member 1400.  The cap member 1600 has an engagement portion 1700 for fixing the recording head to an ink jet recording apparatus.


FIG. 9 is an exploded view of another recording head that can be used for the present invention.  The recording head shown in FIG. 9 is integrated with an ink tank as in the case of FIG. 8.  Multiple inks different from each other in color (such
as cyan, magenta, and yellow inks) can be mounted on a recording head 1001, and the recording head is replaced when mounted ink is consumed.


The recording head 1001, which is intended for the ejection of multiple inks different from each other in color (such as cyan, magenta, and yellow inks), includes a recording element substrate 1100 on which ink supply orifices for cyan, magenta,
and yellow are formed in parallel.  An ink supply/hold member 1400 has a space for independently holding absorbents 1501, 1502, and 1503 for generating negative pressures for holding cyan, magenta, and yellow inks in the absorbents to provide a function
as an ink tank, and forms an independent ink flow path for introducing each ink to the ink supply orifices of the recording element substrate 1100 to provide an ink supply function.


(Recording Unit)


An example of a recording unit suitable for performing recording by means of the ink according to the present invention includes a recording unit including an ink storage portion for storing the ink and a recording head.  In particular, a
recording unit in which the recording head applies thermal energy corresponding to a recording signal to the ink to generate an ink droplet by virtue of the energy can be exemplified.


(Ink Jet Recording Apparatus)


An example of a recording apparatus suitable for performing recording by means of the ink according to the present invention includes a recording apparatus in which thermal energy corresponding to a recording signal is applied to ink in the
chamber of a recording head having an ink storage portion for storing the ink to generate an ink droplet by virtue of the energy.


Hereinafter, the schematic constitution of a mechanism portion of an ink jet recording apparatus will be described.  A recording apparatus main body is constituted by a sheet feeding portion, a sheet conveying portion, a carriage portion, a sheet
discharge portion, and a cleaning portion, and an external packaging portion for protecting them and providing them with design to achieve a role of each mechanism.  Hereinafter, the outline of each of them will be described.


FIG. 2 is a perspective view of a recording apparatus.  FIGS. 2 and 3 are views for explaining the internal mechanism of a recording apparatus main body.  FIG. 2 is a perspective view seen from an upper right portion, and FIG. 3 is a side
sectional view of the recording apparatus main body.


When a sheet is to be fed in the recording apparatus, only a predetermined number of recording media are sent to a nip portion composed of a sheet feeding roller M2080 and a separating roller M2041 in the sheet feeding portion including a sheet
feeding tray M2060.  The sent recording media are separated at the nip portion, and only the uppermost recording medium is conveyed.  The recording medium sent to the sheet conveying portion is guided by a pinch roller holder M3000 and a paper guide
flapper M3030 to be sent to a roller pair composed of a conveying roller M3060 and a pinch roller M3070.  The roller pair composed of the conveying roller M3060 and the pinch roller M3070 are rotated by the driving of an LF motor E0002, and the rotation
causes the recording medium to be conveyed on a platen M3040.


In the carriage portion, when an image is to be formed on a recording medium, a recording head H1001 (FIG. 4) is arranged at a target image forming position, and ink is ejected to the recording medium in accordance with a signal from an
electrical substrate E0014.  Details about the constitution of the recording head H1001 will be described later.  While recording is performed by the recording head H1001, recording main scanning in which a carriage M4000 scans in a column direction and
sub scanning in which a recording medium is conveyed in a row direction by the conveying roller M3060 are alternately repeated, whereby an image is formed on the recording medium.


Finally, the recording medium on which an image has been formed is sandwiched at a nip between a first sheet discharge roller M3110 and a spur M3120 in the sheet discharge portion, conveyed, and discharged to a sheet discharge tray M3160.


In the cleaning portion when a pump M5000 is allowed to act in a state where a cap M5010 is brought into close contact with an ink ejection orifice of the recording head H1001 for the purpose of cleaning the recording head H1001 before and after
image recording, unnecessary ink and the like are sucked from the recording head H1001.  The ink remaining in the cap M5010 is sucked with the cap M5010 opened, whereby neither adhesion of the remaining ink nor a subsequent harmful effect occurs.


(Constitution of Recording Head)


The constitution of a head cartridge H1000 will be described.  The head cartridge H1000 includes the recording head H1001, means for mounting ink tanks H1900, and means for supplying ink from the ink tanks H1900 to the recording head, and is
detachably mounted on the carriage M4000.


FIG. 4 shows how the ink tanks H1900 are mounted on the head cartridge H1000.  The recording apparatus forms an image by means of yellow, magenta, cyan, black, pale magenta, pale cyan, and green inks, so the ink tanks H1900 are independently
prepared for seven colors.  The ink according to the present invention is used for at least one of the above inks.  In addition, as shown in the figure, each ink tank is detachable to the head cartridge H1000.  The ink tanks H1900 can be detached in a
state where the head cartridge H1000 is mounted on the carriage M4000.


FIG. 5 shows an exploded perspective view of the head cartridge H1000.  In the figure, the head cartridge H1000 includes a first recording element substrate H1000, a second recording element substrate H1101, a first plate H1200, a second plate
H1400, an electric wiring substrate H1300, a tank holder H1500, a flow path forming member H1609, a filter H1700, and a seal rubber H1800.


Each of the first recording element substrate H1100 and the second recording element substrate H1101 is an Si substrate having multiple recording elements (nozzles) for ejecting ink formed on one surface by means of photolithography.  Electric
wiring made of Al or the like for supplying power to each recording element is formed by means of a film formation technique, and multiple ink flow paths corresponding to the individual recording elements are also formed by means of photolithography. 
Furthermore, ink supply orifices for supplying ink to the multiple ink flow paths are formed so as to open on the rear surface.


FIG. 6 is an enlarged front view for explaining the constitution of each of the first recording element substrate H1100 and the second recording element substrate H1101.  Reference symbols H2000 to H2600 denote recording element trains (which may
hereinafter be also referred to as nozzle trains) corresponding to different ink colors.  The first recording element substrate H1100 has nozzle trains for three colors: the nozzle train H2000 to which yellow ink is supplied, the nozzle train H2100 to
which magenta ink is supplied, and the nozzle train H2200 to which cyan ink is supplied.  The second recording element substrate H1101 has nozzle trains for four colors: the nozzle train H2300 to which pale cyan ink is supplied, the nozzle train H2400 to
which black ink is supplied, the nozzle train H2500 to which orange ink is supplied, and the nozzle train H2600 to which pale magenta ink is supplied.


Each nozzle train is constituted by 768 nozzles arranged at an interval of 1,200 dpi (dot/inch; reference value) in the direction in which a recording medium is conveyed (hereinafter, referred to as the conveying direction), and each nozzle
ejects about 2 pl of ink.  An opening area in each nozzle ejection orifice is set to about 100 .mu.m.sup.2.  The first recording element substrate H1100 and the second recording element substrate H1101 are bonded and fixed to the first plate H1200 having
formed thereon ink supply orifices H1201 for supplying ink to the first recording element substrate H1100 and the second recording element substrate H1101.


The second plate H1400 having openings is also bonded and fixed to the first plate H1200.  The second plate H1400 holds the electric wiring substrate H1300 in such a manner that the electric wiring substrate H1300, and the first recording element
substrate H1100 and the second recording element substrate H1101 are electrically connected.


The electric wiring substrate H1300 applies an electrical signal for causing each of the nozzles formed on the first recording element substrate H1100 and the second recording element substrate H1101 to eject ink.  The electric wiring substrate
H1300 has: electric wiring corresponding to each of the first recording element substrate H1100 and the second recording element substrate H1101; and an external signal input terminal H1301 which is positioned at an end portion of the electric wiring to
receive an electrical signal from the recording apparatus main body.  The external signal input terminal H1301 is positioned and fixed to the back surface side of the tank holder H1500.


Meanwhile, the flow path forming member H1600 is fixed by means of, for example, ultrasonic welding to the tank holder H1500 for holding the ink tanks H1900.  Thus, an ink flowpath H1501 passing from the ink tanks H1900 to the first plate H1200
is formed.


The filter H1700 is arranged at an end portion on the ink tank side of the ink flow path H1501 engaged with the ink tanks H1900, so the filter H1700 prevents dust from entering from the outside.  The seal rubber H1800 is mounted on the portion at
which the ink flow path H1501 is engaged with the ink tanks H1900 to prevent ink from evaporating from the portion.


Furthermore, as described above, the head cartridge H1000 is constituted by connecting through bonding or the like a tank holder portion constituted by the tank holder H1500, the flow path forming member H1600, the filter H1700, and the seal
rubber H1800, and the recording head portion H1001 constituted by the first recording element substrate H1100, the second recording element substrate H1101, the first plate H1200, the electric wiring substrate H1300, and the second plate H1400.


Description has been made here by taking, as an example of an embodiment of a recording head, a recording head according to a bubble jet (registered trademark) system that performs recording by means of an electrothermal transducer (recording
element) for generating thermal energy for causing ink to generate film boiling in accordance with an electrical signal.


The representative structure and principle of a bubble jet system are preferably basic principles disclosed in, for example, descriptions of U.S.  Pat.  No. 4,723,129.  and U.S.  Pat.  No. 4,740,796.  The method is applicable to any one of
so-called an on-demand type and a continuous type.  In particular, the method is effective for the on-demand type because of the following reason.  At least one driving signal which corresponds to recording information and causes a sudden increase in
temperature exceeding nuclear boiling is applied to an electrothermal transducer arranged in correspondence with a sheet or liquid flow path holding a liquid (ink), to thereby cause the electrothermal transducer to generate thermal energy.  Then, a
thermal action surface of a recording head is caused to generate film boiling.  As a result, an air bubble in the liquid (ink) can be formed so as to be in one-to-one correspondence with the driving signal.  The growth and contraction-of the air bubble
cause the liquid (ink) to be ejected through an opening for ejection, thereby forming at least one droplet.  The driving signal is more preferably of a pulse shape because the growth and contraction of an air bubble can be performed immediately and
appropriately, and hence the liquid (ink) can be ejected with excellent responsiveness.


An example of a second embodiment of an ink jet recording apparatus utilizing mechanical energy includes anon-demand ink jet recording head including: a nozzle forming substrate having multiple nozzles; pressure generating means arranged so as to
be opposed to the nozzles and composed of a piezoelectric material and a conductive material; and ink filling the surroundings of the pressure generating means, in which the pressure generating means is displaced by an applied voltage to eject a small
ink droplet from a nozzle.


The ink jet recording apparatus is not limited to such apparatus as described above in which a head and an ink tank are separated, and may be one in which a head and an ink tank are integrated so that they are unseparable.  The ink tank may be
separably or unseparably integrated with the head to be mounted on a carriage, or may be mounted at a fixing portion of an apparatus to supply ink to a recording head through an ink supply member such as a tube.  When the ink tank is provided with a
constitution for applying a preferable negative pressure to the recording head, an absorber may be arranged in an ink storage portion of the ink tank, or the ink tank may have a flexible ink storage bag and a spring portion for applying bias to expand
the internal volume of the bag.  The recording apparatus may adopt a serial recording system as described above, or may be in the form of a line printer obtained by aligning recording elements over the range corresponding to the entire width of a
recording medium.


(Color Fading Balance)


The term "color fading balance" as used herein refers to the deterioration of an image density and a hue with time in an image of the yellow ink according to the present invention, an image of the cyan and magenta inks to be used in combination
with the yellow ink, and an image with a secondary or tertiary color formed by means of the inks.


FIG. 1 shows an image of the deterioration of an image density with time in the present invention.  In FIG. 1, the axis of abscissa indicates the period during which an image formed by means of each ink is stored, and the axis of ordinate
indicates the image density of the image formed by means of each ink.  In general, an image formed by means of any ink tends to have a lower image density as the image is stored for a longer period.  At this time, if a change with time in the image
density of an image formed by means of each ink constituting an ink set significantly differs from ink to ink, a color fading balance can be said to be poor.


Here, as shown in FIG. 1, the present invention is characterized in that a reduction in image density due to a change with time in each of an image of the yellow ink according to the present invention (.DELTA.  in FIG. 1), an image of the cyan
and magenta inks to be used in combination with the yellow inks (.diamond.  in FIG. 1), and an image with a secondary or tertiary color formed by means of the inks (.quadrature.  in FIG. 1) is in a constant range at all times (the range indicated by
broken lines in FIG. 1).  In other words, with the constitution of the present invention, an image with a uniformized color fading balance at any time point in the period during which the image is stored can be obtained.


EXAMPLES


Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.  However, the present invention is not limited to the following examples unless the examples depart from the gist of the present
invention.  Unless otherwise stated, the term "part(s)" of each ink component in examples and comparative examples represents "part(s) by mass".


(Synthesis of Coloring Material)


(Coloring Material for Yellow Ink)


Diazotized 4-nitro-4'-aminostilbene-2,2-disulfonic acid and 3-aminonaphthalene-1-sulfonic acid were subjected to coupling.  The resultant was turned into a triazole, and a nitro group of the triazole was reduced to an amino group by means of a
conventionally known method to produce aminostilbene-triazole.  Aminostilbene-triazole was dissolved into water, and sodium nitrite and hydrochloric acid were added dropwise to the solution to perform diazotization.  The resultant was added dropwise to
an aqueous solution of a compound represented by the following formula (.alpha.), and the whole was subjected to coupling, followed by dialysis with sodium chloride.  The compound was diazotized with an aqueous solution of sodium nitrite, and was turned
into a triazole by adding an aqueous solution of 6-aminonaphthalene-2-sulfonic acid.  The triazole was dialyzed with sodium chloride to prepare a coloring material represented by the following formula (Y-a).


 ##STR00036##


(Coloring Material for Magenta Ink)


A compound represented by the following formula (.beta.), sodium carbonate, and ethyl benzoyl acetate were allowed to react to one another in xylene, and the reactant was filtered and washed.  To the resultant, were sequentially added with
m-amino acetonitride, copper acetate, and sodium carbonate in N,N-dimethylformamide to carry out a reaction, and the reactant was filtered and washed.  The resultant was sulfonated in fuming sulfuric acid, and the resultant was filtered and washed.  The
resultant was subjected to a condensation reaction with cyanuric chloride in the presence of sodium hydroxide.  Anthranilic acid was added to the reaction liquid to carry out a condensation reaction in the presence of sodium hydroxide.  The resultant was
filtered and washed to prepare a coloring material represented by the following formula (M-a).


 ##STR00037##


(Coloring Material for Cyan Ink)


Sulfolane, monosodium 4-sulfophthalate, ammonium chloride, urea, ammonium molybdate, and copper (II) chloride were mixed, stirred, and washed with methanol.  After that water was added to the resultant, and an aqueous solution of sodium hydroxide
was used to adjust the pH of the solution to 11.  An aqueous solution of hydrochloric acid was added to the resultant solution under stirring, and then sodium chloride was gradually added to precipitate crystals.  The resultant crystals were filtered out
and washed with a 20% aqueous solution of sodium chloride, and then methanol was added.  The precipitated crystals were filtered out, washed with a 70% aqueous solution of methanol, and dried to prepare tetrasodium copper phthalocyanine.  tetrasulfonate
as blue crystals.


Tetrasodium copper phthalocyanine tetrasulfonate thus prepared was gradually added to chlorosulfonic acid, and then thionyl chloride was added dropwise to perform reaction.  After that, the reaction solution was cooled, and the precipitated
crystals were filtered to prepare a wet cake of copper phthalocyanine tetrasulfonic chloride.


Lipal OH, cyanuric-chloride, and monosodium aniline-2,5-disulfonate were added to ice water, and were allowed to react while an aqueous solution of sodium hydroxide was added.  Next, an aqueous solution of sodium hydroxide was added to the
reaction solution to adjust the pH of the reaction solution to 10.  28% ammonia water and ethylenediamine were added to the reaction solution to perform reaction.  Sodium chloride and concentrated hydrochloric acid were added to the resultant reaction
solution to precipitate crystals.  The precipitated crystals were filtered and fractionated, and was washed with a 20% aqueous solution of sodium chloride to prepare a wet cake.  Methanol and water were added to the resultant wet cake, and the whole was
filtered, washed with methanol, and dried to prepare a compound represented by a formula (.gamma.).


The wet cake of copper phthalocyanine tetrasulfonic chloride synthesized in the above was added to an ice water, and the whole was stirred to prepare a suspension.  Ammonia water and the compound represented by formula (.gamma.) synthesized in
the above were added to the suspension to perform reaction.  Water and sodium chloride were added to the mixture to precipitate crystals.  The resultant crystals were filtered, washed with an aqueous solution of sodium chloride, and filtered again,
washed, and dried to prepare a coloring material represented by a formula (C-a) as a blue crystal.  The foregoing reaction allows one to assume that the coloring material has an average number of substituents in the formula (C-a) of l=0, m=1.0 to 2.0, or
n=2.0 to 3.0.


 ##STR00038##


(Preparation of Ink)


(Preparation of Yellow Ink)


The respective components shown in Table 2 below were mixed and sufficiently stirred.  After that, the resultant was filtered through a membrane filter having a pore size of 0.2 .mu.m under pressure to prepare each of yellow inks Y1 to Y5.


 TABLE-US-00002 TABLE 2 Yellow Ink Y1 Y2 Y3 Y4 Y5 Coloring A group C.I.  Direct 2.5 2.0 material Yellow 132 C.I.  Direct 1.0 5.0 Yellow 173 B group Formula (Y-a) 0.5 C.I.  Direct 1.0 Yellow 86 C.I.  Direct 3.0 4.0 Yellow 142 Water- Glycerin 10.0
10.0 10.0 soluble Ethylene glycol 3.0 2.0 organic Polyethylene glycol 200 10.0 10.0 solvent Diethylene glycol 5.0 4.0 4.0 4.0 5.0 Triethylene glycol 2.0 N-methyl-2-pyrrolidone 3.0 3.0 3.0 4.0 Urea 8.0 8.0 8.0 8.0 8.0 Acetylenol EH (*) 0.6 0.6 0.6 0.6 0.6
Isopropanol 3.0 3.0 3.0 3.0 3.0 Ion-exchanged water 67.4 68.4 65.4 66.4 63.4 (*) Ethylene oxide adduct of acetylene glycol (manufactured by Kawaken Fine Chemicals Co., Ltd.; surfactant)


(Preparation of Magenta Ink)


The respective components shown in Table 3 below were mixed and sufficiently stirred.  After that, the resultant was filtered through a membrane filter having a pore size of 0.2 .mu.m under pressure to prepare a magenta ink M1.


 TABLE-US-00003 TABLE 3 Magenta Ink M1 Coloring material Formula (M-a) 5.0 Water-soluble Glycerin 6.0 organic solvent Ethylene glycol 5.0 Polyethylene glycol 200 2.0 Diethylene glycol 3.0 Triethylene glycol N-methyl-2-pyrrolidone Urea 8.0
Acetylenol EH (*) 0.8 Isopropanol 2.5 Ion-exchanged water 67.7 (*) Ethylene oxide adduct of acetylene glycol (manufactured by Kawaken Fine Chemicals Co., Ltd.; surfactant)


(Preparation of Cyan Ink)


The respective components shown in Table 4 below were mixed and sufficiently stirred.  After that, the resultant was filtered through a membrane filter having a pore size of 0.2 .mu.m under pressure to prepare each of cyan inks C1 and C2.


 TABLE-US-00004 TABLE 4 Cyan Ink C1 C2 Coloring material Formula (C-a) 5.0 Exemplified Compound C1 5.0 Water-soluble Glycerin 10.0 6.0 organic solvent Ethylene glycol 6.0 6.0 Polyethylene glycol 200 3.0 Diethylene glycol Triethylene glycol 2.0
2.0 N-methyl-2-pyrrolidone 5.0 5.0 Urea 10.0 10.0 Acetylenol EH (*) 0.5 0.6 Isopropanol 3.0 2.5 Ion-exchanged water 58.5 59.9 (*) Ethylene oxide adduct of acetylene glycol (manufactured by Kawaken Fine Chemicals Co., Ltd.; surfactant)


Exemplified Compound C1 is a coloring material having the following structure.


 ##STR00039##


(A Combination of Ink for Evaluation and Ink to be Used in Combination Therewith)


The yellow inks Y1 to Y5, the magenta ink M1, and the cyan inks C1 and C2 thus prepared were combined as shown in Table 5 below.


 TABLE-US-00005 TABLE 5 Ink for Ink to be used in combination evaluation with ink for evaluation Yellow Cyan Magenta Example 1 Y1 C1 -- 2 Y2 C2 -- 3 Y3 C1 -- 4 Y1 -- M1 5 Y2 -- M1 6 Y3 -- M1 7 Y1 C1 M1 8 Y2 C2 M1 9 Y3 C1 M1 Comparative Example 1
Y4 C2 -- 2 Y5 C1 -- 3 Y4 -- M1 4 Y5 -- M1 5 Y4 C2 M1 6 Y5 C1 M1


(Evaluation of Environmental Gas Resistance)


An ink jet recording apparatus (trade name: Pixus 950i; manufactured by CANON Inc.) was filled with any one of the combinations of the respective inks thus prepared shown in Table 5 to print, on a recording medium (trade-name: PR-101;
manufactured by CANON Inc.), each of an image having an initial reflection density of a yellow ink alone of 1.0, an image having a total duty of 100% (each of a yellow ink and a cyan ink accounted for 50% thereof), an image having a total duty of 100%
(each of a yellow ink and a magenta ink accounted for 50% thereof), and an image having an initial reflection density of composite black composed of three colors (that is, a yellow ink, a magenta ink, and a cyan ink) of 1.0 as test samples.


Each of the test samples thus prepared was placed in a chamber of a gaseous corrosion tester GH-180 (manufactured by Yamasaki-Seiki Co, Ltd.), and was exposed for 432 hours under the conditions of: a temperature of 24.degree.  C.; a humidity of
60%; an ozone gas concentration of 1.2 ppm; an NO.sub.x concentration of 1.25 ppm; an SO.sub.2 concentration of 0.3 ppm; and a gas flow rate of 2 L/min.


After the exposure test, the concentration remaining degree of a yellow ink alone, a secondary color composed of a yellow ink and a cyan ink, a secondary color composed of a yellow ink and a magenta ink, and a color fading balance in composite
black were measured.  A Spectorino (manufactured by Gretag Macbeth) was used for measuring a reflection density.


A concentration remaining degree was calculated from the following expression.  Concentration remaining degree=(Reflection density after exposure test/Reflection density before exposure test).times.100 (%)


In addition, a color fading balance was evaluated on the basis of a .DELTA.OD value in each of: an image with a secondary color composed of a yellow ink and a cyan ink; an image with a secondary color composed of a yellow ink and a magenta ink;
and an image with composite black.  The .DELTA.OD value refers to a difference between the maximum concentration remaining degree and minimum concentration remaining degree of each of a yellow component, a cyan component, and a magenta component in an
image with a secondary color or in an image with composite black.  A large .DELTA.OD value means a bad color fading balance because a hue shifts to any one of the yellow component, the cyan component, and the magenta component.


A .DELTA.OD value was calculated from the following expression.


.DELTA.OD=(Maximum concentration remaining degree of each color component in an image with a secondary color or in an image with composite black)-(Minimum concentration remaining degree of each color component in an image with a secondary color
or in an image with composite black)


Environmental gas resistance was evaluated according to the following criteria on the basis of the concentration remaining degree and the .DELTA.OD value thus obtained.


(1) Concentration remaining degree of yellow ink alone


A: A concentration remaining degree is 70% or more.


B: A concentration remaining degree is 65% or more and less than 70%.


C: A concentration remaining degree is less than 65%.


(2) Color fading balance


A: .DELTA.OD is less than 10.


B: .DELTA.OD is 10 or more and less than 15.


C: .DELTA.OD is 15 or more.


 TABLE-US-00006 TABLE 6 Environmental gas resistance Concentration remaining Color fading degree of yellow ink alone balance Example 1 A A 2 A A 3 A A 4 A A 5 A A 6 A A 7 A A 8 A A 9 A A Comparative Example 1 A C 2 C A 3 A C 4 C A 5 A C 6 C A


The foregoing has shown the following.  In each of Comparative Examples 1, 3, and 5 each involving the use of only a coloring material belonging to the A group as a coloring material of a yellow ink, the color fading ratio of the yellow ink was
lower than those of a magenta ink and a cyan ink, so there was a tendency in that a color fading balance was lost and an image became strongly yellowish in its entirety.  In addition, in each of Comparative Examples 2, 4, and 6 each involving the use of
only a coloring material belonging to the B group as a coloring material of a yellow ink, the yellow ink, the magenta ink, and the cyan ink can be arranged into the magenta ink, the cyan ink, and the yellow ink in order of decreasing degree of color
fading in each color, so a color fading balance was good, but the concentration remaining degree of the yellow ink alone was low, and the color fading of a yellow portion in an entire image was remarkable.  In addition, the use of such coloring material
as specified in the present invention for each ink provided an image with excellent light resistance.


This application claims priorities from Japanese Patent Application Nos.  2004-221836 filed on Jul.  29, 2004 and 2005-216228 filed on Jul.  26, 2005, which are hereby incorporated by reference herein.


* * * * *























				
DOCUMENT INFO
Description: 1. Field of the InventionThe present invention relates to an ink jet yellow ink, an ink set, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus each of which is capable of providing an image excellent in image storagestability, especially environmental gas resistance and light resistance.2. Related Background ArtAn ink jet recording method is a recording method of applying a small ink droplet to any one of recording media such as plain paper and glossy media to form an image, and had become rapidly widespread owing to a reduction in costs and improvementin its recording rate. With the rapid spread of digital cameras in addition to an improvement in quality of images recorded by the method, the method has been generally used as a method of outputting photographic images comparable to the silver halidephotograph.In recent years, image quality has undergone improvement more than ever owing to, for example, extreme reduction in size of an ink droplet and an improvement of color gamut involved in the introduction of multi-color ink. Meanwhile, there havebeen growing demands for coloring materials and inks, and stricter properties have been required in respect of improvement of color developability and reliability concerning anti-clogging or ejection stability.Meanwhile, the ink jet recording method is problematic in terms of, for example, the image storage stability of the resultant recorded article. In general, the recorded article obtained by means of the ink jet recording method is inferior inimage storage stability to the silver halide photograph, and involves the emergence of a problem in that a coloring material on the recorded article is apt to deteriorate to cause a change in color tone of an image and the color fading of the image whenthe recorded article is exposed to light, humidity, heat, an environmental gas present in the air, or the like for a long period of time.A large number of proposals have been co